CN114728812A - Method for preparing positive electrode active material precursor for lithium secondary battery, positive electrode active material precursor, and positive electrode active material, positive electrode, and lithium secondary battery prepared by using the same - Google Patents

Method for preparing positive electrode active material precursor for lithium secondary battery, positive electrode active material precursor, and positive electrode active material, positive electrode, and lithium secondary battery prepared by using the same Download PDF

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CN114728812A
CN114728812A CN202180006530.5A CN202180006530A CN114728812A CN 114728812 A CN114728812 A CN 114728812A CN 202180006530 A CN202180006530 A CN 202180006530A CN 114728812 A CN114728812 A CN 114728812A
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active material
positive electrode
electrode active
material precursor
nickel
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金铉旭
李应周
金佑玹
崔相洵
金俊吉
柳景日
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LG Chem Ltd
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Abstract

The present invention relates to a method for preparing a positive electrode active material precursor in which particle growth of the (001) plane is suppressed; a positive electrode active material precursor prepared by the above method; a positive electrode active material prepared by using the positive electrode active material; a positive electrode containing the positive electrode active material; and a lithium secondary battery.

Description

Method for preparing positive electrode active material precursor for lithium secondary battery, positive electrode active material precursor, and positive electrode active material, positive electrode, and lithium secondary battery prepared by using the precursor
Technical Field
The present application claims priority from korean patent application No. 10-2020-0034381, filed on 20/3/2020, the contents of which are incorporated herein by reference.
The present invention relates to a method of preparing a positive electrode active material precursor for a lithium secondary battery, a positive electrode active material precursor prepared by the above method, and a positive electrode active material, a positive electrode and a lithium secondary battery prepared by using the positive electrode active material precursor.
Background
As the technology development and demand of mobile devices have increased, the demand for secondary batteries as an energy source has significantly increased. Among these secondary batteries, lithium secondary batteries having high energy density, high voltage, long cycle life and low self-discharge rate have been commercialized and widely used.
Lithium transition metal composite oxides have been used as positive electrode active materials for lithium secondary batteries, and among these oxides, lithium cobalt composite metal oxides such as LiCoO having high operating voltage and excellent capacity characteristics are mainly used2. However, LiCoO2Have poor thermal properties due to an unstable crystal structure caused by delithiation. Furthermore, because of LiCoO2Is expensive, so that a large amount of LiCoO is used2There is a limitation as a power source for applications such as electric vehicles.
Lithium manganese complex metal oxides (LiMnO) have been developed2Or LiMn2O4) Lithium iron phosphate compound (LiFePO)4Etc.) or lithium nickel composite metal oxide (Li)NiO2Etc.) as an alternative to LiCoO2The material of (1). Among these materials, research and development have been more actively conducted on lithium nickel composite metal oxides that can easily realize a large capacity battery due to a high reversible capacity of about 200 mAh/g. However, LiNiO2Is limited by the presence of LiCoO2In contrast, LiNiO2Has worse thermal stability, and when an internal short circuit occurs in a charged state due to external pressure, the positive electrode active material itself is decomposed, thereby causing rupture and ignition of the battery. Therefore, LiNiO is maintained as a substance2A lithium transition metal oxide in which a portion of nickel (Ni) is replaced with cobalt (Co), manganese (Mn), or aluminum (Al) has been developed as a method of improving low thermal stability while having excellent reversible capacity.
In order to prepare a cathode active material having a target electrochemical property, it is important to accurately identify the crystallographic characteristics of a precursor used to prepare the cathode active material.
Therefore, it is required to develop a method of controlling the crystallographic characteristics of the precursor particles of the positive electrode active material.
Disclosure of Invention
Technical problem
An aspect of the present invention provides a method of preparing a positive electrode active material precursor, which can suppress growth of a (001) plane.
Another aspect of the present invention provides a positive electrode active material precursor, wherein the growth of the (001) plane can be suppressed, prepared by the above-described preparation method.
Another aspect of the present invention provides a positive electrode active material in which growth of a (003) plane is minimized.
Another aspect of the present invention provides a positive electrode for a lithium secondary battery, including the positive electrode active material.
Another aspect of the present invention provides a lithium secondary battery including the positive electrode for a secondary battery.
Technical scheme
According to an aspect of the present invention, there is provided a method of preparing a positive active material precursor, the method including: a first step of preparing an aqueous transition metal solution containing a nickel raw material, a cobalt raw material, and a manganese raw material; a second step of preparing a reaction mother liquor by adding an ammonium cation complexing agent, an alkaline compound and water to the reactor; a third step of forming a reaction solution by adding the aqueous transition metal solution, an ammonium cation complexing agent, and a basic compound to the reactor containing the reaction mother liquor, and co-precipitating the reaction solution to form a core of a positive electrode active material precursor particle; a fourth step of adjusting the pH of the reaction solution to be higher than the pH of the reaction solution of the third step to grow the positive electrode active material precursor particles; and a fifth step of stabilizing the positive electrode active material precursor particles.
According to another aspect of the present invention, there is provided a positive active material precursor including nickel, cobalt, and manganese, wherein the positive active material precursor satisfies [ formula 1] and [ formula 2 ].
[ formula 1]
2.5≤C(100)/C(001)≤5.0
[ formula 2]
1.0≤C(101)/C(001)≤3.0
In [ formula 1]]And [ formula 2]]In, C(001)Is the grain size in the (001) plane, C(100)Is the grain size in the (100) plane, and C(101)Is the grain size in the (101) plane.
According to another aspect of the present invention, there is provided a positive electrode active material prepared by using the positive electrode active material precursor.
According to another aspect of the present invention, there is provided a positive electrode for a lithium secondary battery, including the positive electrode active material.
According to another aspect of the present invention, there is provided a lithium secondary battery comprising the positive electrode.
Advantageous effects
According to the present invention, since a stabilization step is included during the preparation of the cathode active material precursor, the crystal orientation of the cathode active material precursor is controlled such that the growth of a specific crystal plane is minimized, whereby electrochemical performance can be improved when the cathode active material precursor is applied to a battery.
Drawings
Fig. 1 is a schematic view showing a change in the shape of particles of a positive electrode active material precursor according to a preparation step of the positive electrode active material precursor;
fig. 2 shows X-ray diffraction (XRD) patterns of the positive electrode active material precursors prepared in examples 1 and 2 and comparative examples 1 and 2.
Detailed Description
Hereinafter, the present invention will be described in more detail.
It should be understood that the words or terms used in the specification and claims should not be construed as meanings defined in commonly used dictionaries, and it will be further understood that the words or terms should be interpreted as having meanings consistent with their meanings in the background and technical concept of the related art of the present invention on the basis of the principle that the inventor can appropriately define the meanings of the words or terms to best explain the present invention.
Method for preparing precursor of positive active material
The present inventors have found that growth of a positive electrode active material precursor to a specific crystal plane can be suppressed by adding a stabilization step during preparation of the positive electrode active material precursor, thereby completing the present invention.
Specifically, the method for preparing a positive active material precursor according to the present invention includes the steps of: (1) preparing a transition metal aqueous solution containing a nickel raw material, a cobalt raw material, and a manganese raw material (first step); (2) preparing a reaction mother liquor by adding an ammonium cation complexing agent, an alkaline compound and water to a reactor (second step); (3) forming a reaction solution by adding the aqueous transition metal solution, an ammonium cation complexing agent, and a basic compound to the reactor containing the reaction mother liquor, and co-precipitating the reaction solution to form a core of a positive electrode active material precursor particle (third step); (4) adjusting the pH of the reaction solution to be higher than the pH of the reaction solution of the third step to grow the positive electrode active material precursor particles (fourth step); and (5) stabilizing the positive electrode active material precursor particles (fifth step).
Hereinafter, the method of preparing the positive active material precursor according to the present invention will be described in more detail.
(1) Step of preparing an aqueous solution of a transition metal
First, a transition metal aqueous solution containing a nickel raw material, a cobalt raw material, and a manganese raw material is prepared (first step).
The nickel raw material can be Ni (OH)2、NiO、NiOOH、NiCO3·2Ni(OH)2·4H2O、NiC2O2·2H2O、Ni(NO3)2·6H2O、NiSO4、NiSO4·6H2O, a fatty acid nickel salt or a nickel halide, and any one thereof or a mixture of two or more thereof may be used.
The cobalt material can be Co (OH)2、CoSO4、CoOOH、Co(OCOCH3)2·4H2O、Co(NO3)2·6H2O or CoSO4·7H2O, and any one thereof or a mixture of two or more thereof may be used.
The manganese raw material can be: oxides of manganese such as Mn2O3、MnO2And Mn3O4(ii) a Manganese salts such as MnCO3、Mn(NO3)2、MnSO4Manganese acetate, manganese dicarboxylates, manganese citrates and manganese salts of fatty acids; an oxyhydroxide compound; and manganese chloride, and any one of them or a mixture of two or more thereof may be used.
In addition, the transition metal aqueous solution may contain a doping element (M) in addition to nickel, manganese and cobalt1). In this case, M1May include at least one selected from the group consisting of: tungsten (W), molybdenum (Mo), chromium (Cr), zirconium (Zr), titanium (Ti), magnesium (Mg), tantalum (Ta) and niobium (Nb). In the case where the transition metal aqueous solution further contains a doping element, effects of improving the lifetime characteristics, the discharge characteristics, and/or the stability can be obtained.
The transition metal aqueous solution also contains a doping element M1In the case of (1), the doping element M may be optionally further added in the course of preparing the transition metal aqueous solution1The raw materials of (1).
As containing doping elements M1The raw material of (2) may use at least one selected from the following: containing a doping element M1Acetate, sulfate, sulfide, hydroxide, oxide or oxyhydroxide.
For example, the aqueous transition metal solution according to the present invention may include the nickel raw material in an amount such that the amount of nickel based on the total number of moles of transition metals is 60 mol% or more, for example 80 mol% or more. In the case where the amount of nickel in the transition metal aqueous solution satisfies the above range, the capacity characteristics can be further improved.
(2) Step of preparing reaction mother liquor
Next, a reaction mother liquor is prepared by adding an ammonium cation complexing agent, an alkaline compound and water to the reactor (second step).
In this case, the reactor may be a reactor equipped with a filtration device, such as a Continuous Filtration Tank Reactor (CFTR). In the case of using the continuous filtration tank reactor, since a large amount of the cathode active material precursor can be simultaneously prepared in the same-sized reactor, it has advantages in productivity compared to a batch reactor, and it has advantages in quality characteristics compared to a Continuous Stirred Tank Reactor (CSTR) because it exhibits a uniform particle size distribution.
The ammonium cation complexing agent may be at least one selected from the group consisting of: NH (NH)4OH、(NH4)2SO4、NH4NO3、NH4Cl、CH3COONH4And (NH)4)2CO3And may be added to the reactor in the form of a solution in which the above compound is dissolved in a solvent. In this case, as the solvent, water or a mixture of water and an organic solvent (specifically, alcohol or the like) which can be uniformly mixed with water can be used.
Next, the basic compound may be at least one selected from the group consisting of: NaOH, KOH and Ca (OH)2And may be added to the reactor in the form of a solution in which the above compound is dissolved in a solvent. In this case, as the solvent, water or a mixture of water and an organic solvent (specifically, alcohol or the like) which can be uniformly mixed with water can be used.
In the present invention, it is desirable that the pH of the reaction mother liquor is in the range of 11.7 to 11.9. Conventionally, in the preparation of a nickel-cobalt-manganese-based positive electrode active material precursor, a reaction mother liquid is generally formed in such a manner that the pH of the reaction mother liquid is 12 or more. However, according to the studies of the present inventors, in the case where the pH of the reaction mother liquor is adjusted in the range of 11.7 to 11.9 and the precursor is formed, it was found that the growth of the (001) plane of the positive electrode active material precursor was inhibited.
It is desirable that the reaction mother liquor contains a basic compound at a concentration of 0.01mol/L or less, for example, 0.001mol/L to 0.01mol/L, and contains an ammonium cation complexing agent at a concentration of 0.3mol/L to 0.6 mol/L. When the concentrations of the basic compound and the ammonium cation complexing agent in the reaction mother liquor satisfy the above ranges, it is possible to adjust the pH of the reaction mother liquor to a desired range and prepare a precursor in which the crystal size of the (001) plane is minimized by minimizing the surface energy of primary particles formed in a core formation step described later.
(3) Step of forming core of precursor particle of positive electrode active material
Next, a reaction solution is formed by adding the aqueous transition metal solution, the ammonium cation complexing agent, and the basic compound to the reactor containing the reaction mother liquor, and the reaction solution is coprecipitated to form a core of a positive electrode active material precursor particle (third step).
A process of forming the positive electrode active material precursor particles according to the present invention is shown in fig. 1.
When the coprecipitation reaction is started while adding the aqueous transition metal solution, the ammonium cation complexing agent, and the basic compound to the reactor containing the reaction mother liquid, nuclei (nucleation) of the positive electrode active material precursor particles in the form of primary particles are formed, as shown in fig. 1 (a). As the coprecipitation reaction proceeds, the seeds in the form of secondary particles are formed while the nuclei in the form of primary particles are aggregated as shown in fig. 1(b), and the seeds in the form of secondary particles are aggregated to form nuclei (core) of precursor particles as shown in fig. 1 (c). Thereafter, the growth of the particles is performed on the nuclei by a fourth step described later, and as a result, precursor particles are prepared as shown in fig. 1 (d).
The aqueous transition metal solution used in this third step is the aqueous transition metal solution prepared in the above-described first step, and the ammonium cation complexing agent and the basic compound are the same as those used in the second step.
In the core formation step, it is desirable to maintain the pH of the reaction solution in the range of 10.5 to 11.2. In the case where the pH of the reaction solution satisfies the above range, nuclei (nuclei) of the positive electrode active material precursor are formed in the reaction solution, a series of processes in which the nuclei are aggregated to form nuclei (core) can be smoothly performed, and positive electrode active material precursor particles in which the growth of the (001) plane is suppressed can be prepared. In the case where the pH is outside the above range, it may be difficult to achieve a desired final product particle size because nuclei of precursor particles may not be sufficiently formed and the growth of the particles may be slowed down. In addition, it is also not effective in suppressing growth of the (001) plane of the positive electrode active material precursor particles.
According to the studies of the present inventors, by controlling the concentration and input amount of the material in the initial reaction solution, the reaction temperature and/or the mixing speed, it is possible to control the growth of the crystal plane of the cathode active material precursor in a specific direction or suppress the growth. For example, an environment in which the (001) plane has thermodynamically high surface energy can be created by appropriately controlling the addition rate of the transition metal aqueous solution, the basic compound, and/or the ammonium cation complexing agent added to the initial reaction solution, whereby a core of the cathode active material precursor particle in which the growth of the (001) plane is suppressed can be formed.
Specifically, in the third step of forming the core of the positive electrode active material precursor particle, the ratio of the molar concentration of the ammonium cation complexing agent added per unit time to the molar concentration of the transition metal aqueous solution added per unit time (i.e., the molar concentration of the metal aqueous solution added per unit time/the molar concentration of the ammonium cation complexing agent added per unit time) may be 0.2 or more, for example, 0.25 to 0.4.
In the case where the ratio of the amounts of the aqueous metal solution and the ammonium cation complexing agent added in the third step satisfies the above range, since a state in which the strain energy is minimized is generated by matching the lattice constant of the seed crystal with the lattice constant of the newly formed crystal, a precursor in which the growth of the (001) crystal plane is minimized can be formed.
(4) Step of growing precursor particles of positive electrode active material
Next, when the precursor core particles are formed by the above-described process, the pH of the reaction solution is adjusted to be higher than that of the third step to grow the precursor particles (fourth step).
In the fourth step, the pH of the reaction solution may be controlled to be maintained at more than 11.2 and equal to or less than 13, for example, 11.3 to 11.4, for example. If the pH of the reaction solution is raised as described above, the formation of new particles is suppressed, and particle growth in which crystal growth and particle aggregation occur on the surface of previously formed particles occurs preferentially to increase the particle size.
For example, the pH can be adjusted by adjusting the amount of the basic compound to be added.
(5) Stabilization step
When the precursor particles are grown to a desired size by the fourth step, a stabilization step (fifth step) of stabilizing the precursor particles is performed.
The stabilization step is for providing the crystal orientation of the precursor particles, wherein the growth of the precursor particles is insignificant because aggregation of the particles is suppressed in the stabilization step, but the crystal growth is performed along the crystal plane that has grown to provide a preferred orientation of a specific crystal plane, and therefore, the crystal growth on a plane other than the (001) plane can be promoted to minimize the growth of the (001) plane.
Specifically, the stabilization step is a step in which the average particle diameter (D) of the precursor particles50) The growth rate was 0.10 μm/hr or less.
Desirably, the stabilization step is performed for a time greater than 10%, such as 10% to 25%, of the total reaction time of the third and fourth steps. When the stabilization time satisfies the above range, a positive electrode active material precursor in which the growth of the (001) plane is effectively suppressed can be obtained while being economically advantageous.
The third to fifth steps of the present invention may be carried out in a reactor equipped with a filtration device therein, for example, a Continuous Filtration Tank Reactor (CFTR).
In the case of preparing the cathode active material precursor by using the reactor equipped with the filtering device as described above, since the reaction is performed while continuously discharging the filtrate except for the solid content (i.e., precursor particles) in the reaction solution to the outside of the reactor through the filtering device when the reaction solution in the reactor is filled, the raw materials can be continuously supplied. Therefore, a better yield can be obtained as compared with the case of using a batch reactor having the same volume. In addition, in the case of performing a reaction using a reactor equipped with a filtering device, since the reaction is performed while the reaction solution continuously stays in the reactor unlike a Continuous Stirred Tank Reactor (CSTR), the uniformity of quality of the precursor particles is excellent.
Positive electrode active material precursor
Next, the positive electrode active material precursor according to the present invention will be described.
The cathode active material precursor according to the present invention may be prepared by the above-described preparation method of the present invention, and is a cathode active material precursor comprising nickel, cobalt and manganese, wherein it has a grain size satisfying the following [ formula 1] and [ formula 2 ].
[ formula 1]
2.5≤C(100)/C(001)≤5.0
[ formula 2]
1.0≤C(101)/C(001)≤3.0
In [ formula 1]]And [ formula 2]]In (C)(001)Is the grain size in the (001) plane, C(100)Is the grain size in the (100) plane, and C(101)Is in (101) planeThe grain size of (a).
With the positive electrode active material precursor prepared according to the method of the present invention, since the growth of the (001) crystal plane is suppressed, the grain sizes in the (100) and (101) planes are mainly formed, and as a result, the above-described formulas 1 and 2 are satisfied.
Specifically, the crystal grain size in the (001) plane of the positive electrode active material precursor of the present invention is
Figure BDA0003649421410000111
The following are preferred
Figure BDA0003649421410000112
The following are more preferred
Figure BDA0003649421410000113
To
Figure BDA0003649421410000114
The (001) plane of the cathode active material precursor corresponds to the (003) plane of the cathode active material prepared using the cathode active material precursor, wherein the (003) plane of the cathode active material does not serve as a movement path of lithium ions because it is thermodynamically stable and has an electrochemically inert characteristic. With the cathode active material prepared using the cathode active material precursor having a small crystal grain size as in the (001) plane in the present invention, since the growth of the (003) plane is suppressed and the area of the other plane as a lithium movement path is increased, the mobility of lithium ions is increased, whereby when the cathode active material is used in a battery, the capacity and resistance characteristics are further improved due to the increased mobility of lithium ions.
The positive active material precursor according to the present invention may be a nickel-cobalt-manganese hydroxide, a nickel-cobalt-manganese oxyhydroxide, or a mixture thereof, and the molar ratio of nickel in the entire transition metals in the hydroxide or oxyhydroxide may be 60 mol% or more, for example, 80 mol% or more. In the case where the nickel content in the precursor satisfies the above range, excellent capacity characteristics can be obtained.
Method for preparing positive electrode active material
The positive electrode active material precursor in which the growth of the (001) crystal plane was inhibited prepared above and a lithium raw material were mixed and sintered to prepare a positive electrode active material.
The lithium raw material may be used without particular limitation as long as it is a compound containing a lithium source, but preferably at least one selected from the following may be used: lithium carbonate (Li)2CO3) Lithium hydroxide (LiOH. H)2O)、LiNO3、CH3COOLi and Li2(COO)2。
For example, the transition metal element and the lithium raw material contained in the precursor may be mixed in an amount such that the molar ratio of the transition metal (Me) to lithium (Li) is in the range of 1:1 to 1: 1.3. In the case where the lithium raw material is mixed in a ratio less than the above range, the capacity of the prepared cathode active material may be reduced, and in the case where the lithium raw material is mixed in a ratio greater than the above range, since the particles are sintered during the sintering process, the preparation of the cathode active material may be difficult, the capacity may be reduced, and the separation of the cathode active material particles may occur after the sintering.
The sintering may be performed at a temperature in the range of 730 ℃ to 800 ℃ for 10 hours to 15 hours, for example in the range of 750 ℃ to 780 ℃ for 12 hours to 14 hours. With the cathode active material precursor of the present application, since the path through which lithium ions can move is as contacted with the outside as much as possible due to the inhibition of the growth of the (001) plane, the diffusion of lithium ions becomes easy, whereby the sintering can be performed at a lower temperature and for a shorter time than the sintering temperature and time during the preparation of a conventional cathode active material.
Positive electrode active material
Further, the present invention provides a positive electrode active material prepared by using the above positive electrode active material precursor.
Specifically, since the cathode active material according to the present invention is prepared by using a cathode active material precursor in which growth of a (001) plane is suppressed, the cathode active material may be a lithium nickel cobalt manganese-based oxide in which growth of a (003) plane is suppressed, and the (003) plane may not be a movement path of lithium ions.
More specifically, the cathode active material of the present invention may be a lithium nickel cobalt manganese-based oxide represented by the following chemical formula 1.
[ chemical formula 1]
Li1+aNixCoyMnzM1 wO2
In chemical formula 1, M1May be at least one selected from the following: tungsten (W), molybdenum (Mo), chromium (Cr), zirconium (Zr), titanium (Ti), magnesium (Mg), tantalum (Ta), and niobium (Nb).
1+ a represents a molar ratio of lithium in the lithium transition metal oxide, wherein a may satisfy 0. ltoreq. a.ltoreq.0.3, for example 0. ltoreq. a.ltoreq.0.2.
x represents the molar ratio of nickel in the total transition metal, wherein x can satisfy 0.60. ltoreq. x <1.0, 0.70. ltoreq. x.ltoreq.0.99, or 0.80. ltoreq. x.ltoreq.0.99. In the case where the nickel content satisfies the above range, excellent capacity characteristics can be obtained.
y represents the molar ratio of cobalt in the total transition metal, wherein y may satisfy 0< y <0.40, 0< y <0.30, or 0.01. ltoreq. y.ltoreq.0.20.
z represents a molar ratio of manganese in the total transition metal, wherein z may satisfy 0< z <0.40, 0< z <0.30, or 0.01< z < 0.20.
w represents M1The molar ratio among all transition metals, wherein w may satisfy 0. ltoreq. w.ltoreq.0.1 or 0. ltoreq. w.ltoreq.0.05.
Since the area of the (003) plane, which may not be a lithium ion movement path, is minimized in the positive electrode active material of the present invention, the lithium ion mobility is excellent. Thus, when the cathode active material of the present invention is used in a battery, excellent capacity characteristics and resistance characteristics can be obtained.
Positive electrode
In addition, the present invention provides a positive electrode for a lithium secondary battery comprising the positive electrode active material prepared by the above method.
Specifically, the positive electrode includes a positive electrode current collector and a positive electrode active material layer that is disposed on at least one surface of the positive electrode current collector and includes the above-described positive electrode active material.
The positive electrode collector is not particularly limited as long as it has conductivity without causing adverse chemical changes in the battery, and for example: stainless steel, aluminum, nickel, titanium, and calcined carbon; or aluminum or stainless steel surface-treated with one of carbon, nickel, titanium, silver, and the like. In addition, the cathode current collector may generally have a thickness of 3 to 500 μm, and fine irregularities may be formed on the surface of the current collector to improve adhesion of the cathode active material. For example, the positive electrode current collector may be used in various shapes such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven fabric body, and the like.
The positive electrode active material layer may further include a conductive material and a binder, in addition to the positive electrode active material.
In this case, the content of the cathode active material may be 80 to 99 wt%, for example, 85 to 98 wt%, based on the total weight of the cathode active material layer. When the content of the positive electrode active material is within the above range, excellent capacity characteristics may be obtained.
In this case, the conductive material is used to provide conductivity to the electrode, wherein any conductive material may be used without particular limitation so long as it has suitable electron conductivity without causing adverse chemical changes in the battery. Specific examples of the conductive material may be the following: graphite such as natural graphite or artificial graphite; carbon-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, thermal black and carbon fibers; powders or fibers of metals such as copper, nickel, aluminum, and silver; conductive whiskers such as zinc oxide whiskers and potassium titanate whiskers; conductive metal oxides such as titanium oxide; or a conductive polymer such as a polyphenylene derivative, and any one thereof or a mixture of two or more thereof may be used. The content of the conductive material may be generally 1 to 30% by weight, based on the total weight of the positive electrode active material layer.
The binder serves to improve the adhesion between the particles of the positive electrode active material and the adhesion between the positive electrode active material and the current collector. Specific examples of the binder may be polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, Ethylene Propylene Diene Monomer (EPDM), sulfonated EPDM, Styrene Butadiene Rubber (SBR), fluororubber, or various copolymers thereof, and any one or a mixture of two or more thereof may be used. The binder may be contained in an amount of 1 to 30 wt% based on the total weight of the positive electrode active material layer.
The positive electrode may be prepared according to a typical method of preparing a positive electrode, in addition to using the above-described positive electrode active material. For example, the cathode may be prepared by coating a cathode material mixture prepared by dissolving or dispersing the above-described cathode active material and, optionally, a binder and a conductive material in a solvent on a cathode current collector, and then preparing the cathode by drying and roll-pressing the coated cathode current collector, or by casting the cathode material mixture on a separate support, and then laminating a film separated from the support on the cathode current collector. In this case, the types and amounts of the positive electrode active material, the binder, and the conductive material are the same as previously described.
The solvent may be a solvent generally used in the art. The solvent may include dimethyl sulfoxide (DMSO), isopropyl alcohol, N-methylpyrrolidone (NMP), acetone, or water, and any one of them or a mixture of two or more of them may be used. The amount of the solvent used may be sufficient if the solvent may dissolve or disperse the positive electrode active material, the conductive material, and the binder, and may be capable of having a viscosity that may provide excellent thickness uniformity during subsequent coating for preparing the positive electrode, in consideration of the coating thickness of the slurry and the manufacturing yield.
Lithium secondary battery
In addition, in the present invention, an electrochemical device including the cathode may be prepared. The electrochemical device may be, in particular, a battery or a capacitor, and may be, for example, a lithium secondary battery.
The lithium secondary battery specifically includes a positive electrode, a negative electrode disposed facing the positive electrode, a separator disposed between the positive electrode and the negative electrode, and an electrolyte, wherein a detailed description thereof will be omitted because the positive electrode is the same as described above, and only the remaining configuration will be described in detail hereinafter.
In addition, the lithium secondary battery may further optionally include a battery container (which accommodates an electrode assembly of a cathode, an anode and a separator) and a sealing member sealing the battery container.
In a lithium secondary battery, an anode includes an anode current collector and an anode active material layer disposed on the anode current collector.
The anode current collector is not particularly limited as long as it has high conductivity without causing adverse chemical changes in the battery, and for example: copper, stainless steel, aluminum, nickel, titanium and roasted carbon; copper or stainless steel surface-treated with one of carbon, nickel, titanium, silver, and the like; and aluminum-cadmium alloys. In addition, the anode current collector may generally have a thickness of 3 to 500 μm, and similar to the cathode current collector, fine irregularities may be formed on the surface of the current collector to improve adhesion of the anode active material. For example, the anode current collector may be used in various shapes such as a film, a sheet, a foil, a net, a porous body, a foam, a nonwoven fabric body, and the like.
The anode active material layer selectively contains a binder and a conductive material in addition to the anode active material.
A compound capable of reversibly intercalating and deintercalating lithium may be used as the negative electrode active material. Specific examples of the anode active material may be the following: carbonaceous materials such as artificial graphite, natural graphite, graphitized carbon fiber, and amorphous carbon; (semi) metal-based materials capable of forming an alloy with lithium, such as silicon (Si), aluminum (Al), tin (Sn), lead (Pb), zinc (Zn), bismuth (Bi), indium (In), magnesium (Mg), gallium (Ga), cadmium (Cd), Si alloys, Sn alloys, or Al alloys; can be doped and undoped with lithiumOf (semi) metal oxides such as SiOβ(0<β<2)、SnO2Vanadium oxide and lithium vanadium oxide; or a composite material comprising a (semi) metallic material and a carbonaceous material, such as a Si — C composite material or a Sn — C composite material, and any one of them or a mixture of two or more thereof may be used. In addition, a metallic lithium thin film may be used as a negative electrode active material. In addition, low crystalline carbon and high crystalline carbon may be used as the carbon material. Typical examples of the low crystalline carbon may be soft carbon and hard carbon, and typical examples of the high crystalline carbon may be irregular, planar, flaky, spherical or fibrous natural or artificial graphite, kish graphite, pyrolytic carbon, mesophase pitch-based carbon fiber, mesophase carbon microbeads, mesophase pitch, and high-temperature sintered carbon such as petroleum or coal tar pitch-derived coke.
The content of the anode active material may be 80 to 99 wt% based on the total weight of the anode active material layer.
The binder is a component that contributes to the binding between the conductive material, the active material, and the current collector, and is generally added in an amount of 0.1 to 10 wt% based on the total weight of the anode active material layer. Examples of the binder may be polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinyl pyrrolidone, polytetrafluoroethylene, polyethylene, polypropylene, Ethylene Propylene Diene Monomer (EPDM), sulfonated EPDM, styrene butadiene rubber, fluororubber, and various copolymers thereof.
The conductive material is a component for further improving the conductivity of the anode active material, and may be added in an amount of 10 wt% or less, for example, 5 wt% or less, based on the total weight of the anode active material layer. The conductive material is not particularly limited as long as it has conductivity without causing adverse chemical changes in the battery, and conductive materials such as: graphite such as natural graphite or artificial graphite; carbon black such as acetylene black, ketjen black, channel black, furnace black, lamp black and thermal black; conductive fibers such as carbon fibers or metal fibers; a fluorocarbon compound; metal powders such as aluminum powder and nickel powder; conductive whiskers such as zinc oxide whiskers and potassium titanate whiskers; conductive metal oxides such as titanium oxide; or a polyphenylene derivative.
The anode may be prepared by coating an anode material mixture prepared by dissolving or dispersing an anode active material and optionally a binder and a conductive material in a solvent on an anode current collector and drying the coated anode current collector, or may be prepared by casting the anode material mixture on a separate support and then laminating a film separated from the support on the anode current collector.
In the lithium secondary battery, a separator separates an anode and a cathode and provides a moving path of lithium ions, wherein any separator may be used as the separator without particular limitation as long as it is generally used in the lithium secondary battery, and in particular, a separator having a high moisture-retaining ability to an electrolyte and a low resistance to electrolyte ion transfer may be used. Specifically, it is possible to use: porous polymer films, for example, porous polymer films prepared from polyolefin-based polymers such as ethylene homopolymer, propylene homopolymer, ethylene/butene copolymer, ethylene/hexene copolymer, and ethylene/methacrylate copolymer; or have a laminated structure of two or more layers thereof. In addition, a typical porous nonwoven fabric, such as a nonwoven fabric formed of high-melting glass fibers or polyethylene terephthalate fibers, may be used. In addition, a coated separator including a ceramic component or a polymer material may be used to ensure heat resistance or mechanical strength, and a separator having a single-layer or multi-layer structure may be selectively used.
In addition, the electrolyte used in the present invention may include an organic liquid electrolyte, an inorganic liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, or a melt-type inorganic electrolyte, which may be used in the preparation of a lithium secondary battery, but the present invention is not limited thereto.
Specifically, the electrolyte may include an organic solvent and a lithium salt.
Any organic solvent may be used as the organic solvent without particular limitation so long as it can serve as a medium through which ions participating in the electrochemical reaction of the battery can move. Specifically, the following substances may be used as the organic solvent: ester solvents such as methyl acetate, ethyl acetate, gamma-butyrolactone and epsilon-caprolactone; ether solvents such as dibutyl ether or tetrahydrofuran; ketone solvents such as cyclohexanone; aromatic hydrocarbon solvents such as benzene and fluorobenzene; or carbonate-based solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), Ethylene Carbonate (EC), and Propylene Carbonate (PC); alcohol solvents such as ethanol and isopropanol; nitriles such as R-CN (where R is a linear, branched or cyclic C2-C20 hydrocarbyl group and may contain double bonds, aromatic rings or ether linkages); amides such as dimethylformamide; dioxolanes such as 1, 3-dioxolane; or sulfolane. Among these solvents, a carbonate-based solvent may be used, and for example, a mixture of a cyclic carbonate (e.g., ethylene carbonate or propylene carbonate) having high ion conductivity and high dielectric constant, which can improve charge/discharge performance of a battery, and a linear carbonate-based compound (e.g., ethylene carbonate, dimethyl carbonate, or diethyl carbonate) having low viscosity may be used.
The lithium salt may be used without particular limitation as long as it is a compound capable of providing lithium ions used in the lithium secondary battery. Specifically, the following may be used as the lithium salt: LiPF6、LiClO4、LiAsF6、LiBF4、LiSbF6、LiAlO4、LiAlCl4、LiCF3SO3、LiC4F9SO3、LiN(C2F5SO3)2、LiN(C2F5SO2)2、LiN(CF3SO2)2LiCl, LiI or LiB (C)2O4)2. The lithium salt may be used in a concentration range of 0.1M to 2.0M. In the case where the concentration of the lithium salt is included in the above range, since the electrolyte may have appropriate conductivity and viscosity, excellent performance of the electrolyte may be obtained, and lithium ions may be efficiently moved.
In order to improve the life characteristics of the battery, suppress the decrease in the battery capacity, and increase the discharge capacity of the battery, it is possible to use, in addition to the electrolyte componentAdding to the electrolyte at least one additive, for example of halogenated alkylene carbonate type compounds such as ethylene bis-fluorocarbonate, pyridine, triethyl phosphite, triethanolamine, cyclic ethers, ethylenediamine, (glycidyl) dimethyl ethers, hexamethylphosphoric triamide, nitrobenzene derivatives, sulfur, quinone imine dyes, N-substituted
Figure BDA0003649421410000191
Oxazolidinone, N-substituted imidazolidine, ethylene glycol dialkyl ether, ammonium salts, pyrrole, 2-methoxyethanol, or aluminum trichloride. In this case, the additive may be contained in an amount of 0.1 to 5 parts by weight, based on 100 parts by weight of the total weight of the electrolyte.
As described above, since the lithium secondary battery including the positive electrode active material according to the present invention stably exhibits excellent discharge capacity, output characteristics, and capacity retention rate, the lithium secondary battery is suitable for: portable devices such as mobile phones, notebook computers, and digital cameras; and electric vehicles such as Hybrid Electric Vehicles (HEVs).
Therefore, according to another embodiment of the present invention, there are provided a battery module including the lithium secondary battery as a unit cell and a battery pack including the battery module.
The battery module or the battery pack may be used as a power source for at least one of a medium-large-sized device: an electric tool; electric vehicles including Electric Vehicles (EVs), hybrid electric vehicles, and plug-in hybrid electric vehicles (PHEVs); or an electrical power storage system.
The shape of the lithium secondary battery of the present invention is not particularly limited, but a cylindrical type, a prismatic type, a pouch type, or a coin type using a can may be used.
The lithium secondary battery according to the present invention may be used not only in a battery cell used as a power source for a small-sized device, but also as a unit cell in a middle-or large-sized battery module including a plurality of battery cells.
Description of the preferred embodiments
Hereinafter, the present invention will be described in detail based on specific examples. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these exemplary embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
NiSO is added in an amount such that the molar ratio of nickel to cobalt to manganese is 88:5:74、CoSO4And MnSO4Mixed in water to prepare an aqueous transition metal solution (first step).
A container containing the transition metal aqueous solution, another NaOH solution and NH4The aqueous OH solutions were each connected to a 350L Continuous Filtration Tank Reactor (CFTR) equipped with a filtration device (filter).
Subsequently, after 86L of deionized water was placed in the reactor, dissolved oxygen in the water was removed by purging the reactor with nitrogen at a rate of 20L/min to create a non-oxidizing atmosphere in the reactor. Thereafter, aqueous NaOH solution and NH were added4After the OH aqueous solution, while the mixture was stirred at a stirring speed of 700rpm, a reaction mother liquor having a pH of 11.7 to 11.9 was prepared (second step).
Thereafter, the aqueous transition metal solution, NH4An aqueous OH solution and an aqueous NaOH solution are added to the reactor to induce the formation of nickel cobalt manganese hydroxide particles and aggregation of the particles to form precursor nuclei (third step). In this case, an aqueous transition metal solution and NH are added4Aqueous OH solution, so that NH is added per unit time4The ratio of the molar concentration of the aqueous OH solution to the molar concentration of the aqueous transition metal solution was 0.3, and the amount of the aqueous NaOH solution added was adjusted so that the pH of the reaction solution could be maintained at 10.5 to 11.2.
Subsequently, a reaction is performed while adjusting the addition amount of the NaOH aqueous solution so that the pH of the reaction solution is 11.3 to 11.5 to grow nickel cobalt manganese hydroxide particles (fourth step).
The total reaction time of the precursor core formation step (third step) and the particle growth reaction step (fourth step) was 40 hours.
Then, the nickel-cobalt-manganese hydroxide particles after completion of the growth were further reacted for 8 hours to be stabilized (fifth step).
When the reactor was full, the reaction was carried out while continuously discharging the filtrate through the filtration device in the reactor. Next, the nickel-cobalt-manganese hydroxide particles formed through the above process are separated, washed, and then dried to prepare nickel-cobalt-manganese hydroxide particles having Ni mixed therein0.88Co0.05Mn0.07(OH)2And Ni0.88Co0.05Mn0.07Precursors of OOH phases.
Example 2
A cathode active material precursor was prepared in the same manner as in example 1, except that the precursor core formation step (third step) and the particle growth reaction step (fourth step) were performed for a total of 53 hours and the stabilization reaction (fifth step) was performed for 15 hours.
Comparative example 1
NiSO is added in an amount such that the molar ratio of nickel to cobalt to manganese is 88:5:74、CoSO4And MnSO4Mixed in water to prepare an aqueous transition metal solution.
Subsequently, after 86L of deionized water was placed in a Continuous Filtration Tank Reactor (CFTR) equipped with a filtration device (filter), dissolved oxygen in the water was removed by purging the reactor with nitrogen at a rate of 20L/min to create a non-oxidizing atmosphere in the reactor. Thereafter, aqueous NaOH solution and NH were added4After the aqueous OH solution, while the mixture was stirred at a stirring speed of 700rpm, a reaction mother liquor having a pH of 12.1 was prepared.
Adding aqueous solution of transition metal and NH4An aqueous OH solution and an aqueous NaOH solution are added to the reactor to induce the formation of nickel cobalt manganese hydroxide particles and particle aggregation to form precursor nuclei. In this case, an aqueous transition metal solution and NH are added4Aqueous OH solution, so that NH is added per unit time4The ratio of the molar concentration of the aqueous OH solution to the molar concentration of the aqueous transition metal solution was 0.5, and the amount of the aqueous NaOH solution added was adjusted so that the pH of the reaction solution could be maintained at 11.7 to 11.9.
Subsequently, a reaction was performed while adjusting the addition amount of NaOH aqueous solution so that the pH of the reaction solution was 12, to grow nickel cobalt manganese hydroxide particles.
The total reaction time of the precursor core formation step and the particle growth reaction step was 48 hours.
When the reactor was full, the reaction was carried out while continuously discharging the filtrate through the filtration device in the reactor.
Then, the nickel-cobalt-manganese hydroxide particles formed through the above process are separated, washed, and then dried to prepare nickel-cobalt-manganese hydroxide particles having Ni mixed therein0.88Co0.05Mn0.07(OH)2And Ni0.88Co0.05Mn0.07Precursors of OOH phases.
Comparative example 2
A positive electrode active material precursor was prepared in the same manner as in example 1, except that the stabilization step of the nickel-cobalt-manganese hydroxide particles was not performed after the growth was completed.
Experimental example 1 particle characterization
(1) Grain size of the precursor
The grain sizes of the precursor particles of the positive electrode active material prepared in examples 1 and 2 and comparative examples 1 to 2 were measured by the following methods.
The X-ray diffraction (XRD) patterns of the precursors prepared in examples 1 and 2 and comparative examples 1 and 2 were measured using an X-ray diffraction analyzer (Rigaku Corporation). XRD patterns of the positive electrode active material precursor particles prepared in examples 1 and 2 and comparative examples 1 and 2 are shown in fig. 2.
After obtaining the half-value width of the peak of each crystal plane from the measured XRD pattern, the grain size in each crystal plane of the precursor was calculated by ellipsoid modeling using the scherrer equation.
The measurement results are shown in table 1 below.
[ Table 1]
Figure BDA0003649421410000231
As shown in [ table 1], with respect to the cathode active material precursors prepared in examples 1 and 2, it was confirmed that the growth of the (001) crystal plane was suppressed as compared to the cathode active material precursors prepared in comparative examples 1 and 2.
(2) Average particle diameter
In order to examine the particle size distribution of the positive electrode active material precursor particles prepared in examples 1 and 2 and comparative examples 1 and 2, the particle size of the positive electrode active material precursors formed in examples 1 and 2 and comparative examples 1 and 2 was measured using a particle size distribution meter (Microtrac S3500, Microtrac), and the results thereof are shown in [ table 2] below.
(3) BET specific surface area
The positive electrode active material precursors prepared in example 1 and comparative examples 1 and 2 were examined for brunauer-emmett-teller (BET) specific surface area. The specific surface area of the positive electrode active material precursor was measured by the BET method, in particular, the specific surface area was calculated from the nitrogen adsorption amount at a liquid nitrogen temperature (77K) using the bessel orp-mini II of Bell Japan inc, and the result thereof is shown in the following [ table 2 ].
(4) Tap density
After 50g each of the positive electrode active material precursors obtained in examples 1 and 2 and comparative examples 1 and 2 was charged into a 200cc container, the apparent density of the particles, which was obtained by vibrating under constant conditions, was measured. Specifically, the tap density of the lithium transition metal oxide particles was measured using a tap density tester (KYT-5000, Seishin Enterprise co., LTD.). The measurement results are shown in the following [ table 2 ].
[ Table 2]
Figure BDA0003649421410000241
Experimental example 2: initial efficiency
A lithium secondary battery was prepared by using the positive active material precursors of examples 1 and 2 and comparative examples 1 and 2 as prepared in experimental example 1.
Specifically, each of the cathode active material precursors prepared in examples 1 and 2 and comparative examples 1 and 2 was mixed with LiOH in such a manner that the molar ratio of lithium (Li) to transition metal was 1.07:1, and sintered at 770 ℃ for 12 hours to prepare each of the cathode active materials.
Various cathode active materials, conductive materials, and binders prepared as described above were mixed in a solvent to prepare a cathode slurry. One surface of the aluminum current collector was coated with the positive electrode slurry, dried, and then rolled to prepare a positive electrode.
Li metal was used as the negative electrode.
Various lithium secondary batteries were prepared by preparing an electrode assembly by disposing a polyethylene separator between the positive and negative electrodes prepared as described above, disposing the electrode assembly in a battery case, and then injecting an electrolyte into the case. In this case, as the electrolyte, an electrolyte in which 1M LiPF is injected6In an organic solvent in which Ethylene Carbonate (EC), ethylmethyl carbonate (EMC), diethyl carbonate (DEC) were mixed in a volume ratio of 3:4:3, to prepare lithium secondary batteries according to examples 1 and 2 and comparative examples 1 and 2.
Subsequently, each of the lithium secondary batteries prepared in examples 1 and 2 and comparative examples 1 and 2 was charged to 4.25V at 25 ℃ with a constant current of 0.1C. Subsequently, each lithium secondary battery was discharged to 3.0V at a constant current of 0.1C, and the initial charge capacity, the initial discharge capacity, and the initial efficiency of the lithium secondary batteries according to examples 1 and 2 and comparative examples 1 and 2 were confirmed, and the results thereof are shown in table 3 below.
[ Table 3]
Charging capacity (mAh/g) Discharge capacity (mAh/g) Efficiency (%)
Example 1 233.5 214.0 91.6
Example 2 232.0 216.3 93.2
Comparative example 1 229.0 208.9 91.2
Comparative example 2 231.7 213.9 92.3
Experimental example 3: life characteristic
Lithium secondary batteries respectively comprising the cathode active materials of examples 1 and 2 and comparative examples 1 and 2, prepared by the same method as experimental example 2, were charged to 4.25V at a constant current of 0.1C at 45 ℃. Subsequently, each lithium secondary battery was discharged to 3.0V at a constant current of 0.1C. The above charge and discharge was set to 1 cycle, and after repeating the cycle 30 times, the capacity retention rate and the resistance characteristics at the 30 th cycle of the lithium secondary batteries of examples 1 and 2 and comparative examples 1 and 2 were measured, and the results thereof are shown in table 4 below.
[ Table 4]
Capacity retention (%) DCR(％)
Example 1 95.4 63.6
Example 2 96.2 44.2
Comparative example 1 96.0 85.4
Comparative example 2 93.9 64.6
Referring to tables 3 and 4, with the lithium secondary battery of comparative example 1, the initial efficiency was decreased and the resistance after 30 cycles was significantly increased as compared to the lithium secondary batteries of examples 1 and 2, and with the lithium secondary battery of comparative example 2, it was confirmed that the capacity retention rate after 30 cycles was significantly decreased as compared to those of examples 1 and 2. In contrast, the lithium secondary batteries of examples 1 and 2 had excellent initial efficiency and excellent life characteristics.

Claims (16)

1. A method of preparing a positive active material precursor, the method comprising:
a first step of preparing an aqueous transition metal solution containing a nickel raw material, a cobalt raw material, and a manganese raw material;
a second step of preparing a reaction mother liquor by adding an ammonium cation complexing agent, an alkaline compound and water to the reactor;
a third step of forming a reaction solution by adding the aqueous transition metal solution, an ammonium cation complexing agent, and a basic compound to the reactor containing the reaction mother liquor, and co-precipitating the reaction solution to form a core of a positive electrode active material precursor particle;
a fourth step of adjusting the pH of the reaction solution to be higher than the pH of the reaction solution of the third step to grow the positive electrode active material precursor particles; and
a fifth step of stabilizing the positive electrode active material precursor particles.
2. The process of claim 1, wherein the pH of the reaction mother liquor in the second step is in the range of 11.7 to 11.9.
3. The method according to claim 1, wherein the pH of the reaction solution in the third step is in the range of 10.5 to 11.2.
4. The method according to claim 1, wherein the pH of the reaction solution in the fourth step is greater than 11.2 and equal to or less than 11.5.
5. The method according to claim 1, wherein, in the third step, a ratio of a molar concentration of the ammonium cation complexing agent added per unit time to a molar concentration of the transition metal aqueous solution added per unit time is 0.2 or more.
6. The process according to claim 1, wherein, in the second step, the reaction mother liquor contains the basic compound at a concentration of 0.01mol/L or less and the ammonium cation complexing agent at a concentration of 0.3 to 0.6 mol/L.
7. The process of claim 1, wherein the reactor is a reactor equipped with a filtration device.
8. The method according to claim 1, wherein an average particle size growth rate of the positive electrode active material precursor particles in the fifth step is 0.10 μm/hr or less.
9. The method according to claim 1, wherein in the fifth step, the stabilization is performed for 10% or more of the sum of the reaction times of the third step and the fourth step.
10. A positive electrode active material precursor comprising nickel, cobalt and manganese,
wherein the positive electrode active material precursor satisfies [ formula 1] and [ formula 2 ]:
[ formula 1]
2.5≤C(100)/C(001)≤5.0
[ formula 2]
1.0≤C(101)/C(001)≤3.0
Wherein, in [ formula 1] and [ formula 2],
C(001)is the grain size in the (001) plane,
C(100)is the grain size in the (100) plane,
C(101)is the grain size in the (101) plane.
11. The positive electrode active material precursor according to claim 10, wherein the crystal grain size in the (001) plane of the positive electrode active material precursor is
Figure FDA0003649421400000021
The following.
12. The positive active material precursor according to claim 10, wherein the positive active material precursor is a nickel-cobalt-manganese hydroxide, a nickel-cobalt-manganese oxyhydroxide, or a mixture thereof.
13. The positive electrode active material precursor according to claim 11, wherein a molar ratio of nickel in the entire transition metals in the nickel-cobalt-manganese hydroxide and the nickel-cobalt-manganese oxyhydroxide is 60 mol% or more.
14. A positive electrode active material prepared by using the positive electrode active material precursor of claim 10.
15. A positive electrode for a lithium secondary battery, comprising the positive electrode active material according to claim 14.
16. A lithium secondary battery comprising the positive electrode according to claim 15.
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